Sandwich-Type Mixed Tetrapyrrole Rare-Earth Triple-Decker Compounds. Effect of the Coordination Geometry on the Single-Molecule-Magnet Nature

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• 作者：Jinglan Kan ; Hailong Wang ; Wei Sun ; Wei Cao ; Jun Tao ; Jianzhuang Jiang
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：August 5, 2013
• 年：2013
• 卷：52
• 期：15
• 页码：8505-8510
• 全文大小：326K
• 年卷期：v.52,no.15(August 5, 2013)
• ISSN：1520-510X

文摘

Employment of the raise-by-one step method starting from M(TClPP)(acac) (acac = monoanion of acetylacetone) and [Pc(OPh)₈]M鈥瞇Pc(OPh)₈] led to the isolation and free modulation of the two rare-earth ions in the series of four mixed tetrapyrrole dysprosium sandwich complexes {(TClPP)M[Pc(OPh)₈]M鈥瞇Pc(OPh)₈]} [1鈥?b>4; TClPP = dianion of meso-tetrakis(4-chlorophenyl)porphyrin; Pc(OPh)₈ = dianion of 2,3,9,10,16,17,23,24-octa(phenoxyl)phthalocyanine; M鈥揗鈥?= Dy鈥揇y, Y鈥揇y, Dy鈥揧, and Y鈥揧]. Single-crystal X-ray diffraction analysis reveals different octacoordination geometries for the two metal ions in terms of the twist angle (defined as the rotation angle of one coordination square away from the eclipsed conformation with the other) between the two neighboring tetrapyrrole rings for the three dysprosium-containing isostructural triple-decker compounds, with the metal ion locating between an inner phthalocyanine ligand and an outer porphyrin ligand with a twist angle of 9.64鈥?.90掳 and the one between two phthalocyanine ligands of 25.12鈥?5.30掳. Systematic and comparative studies over the magnetic properties reveal magnetic-field-induced single-molecule magnet (SMM), SMM, and non-SMM nature for 1鈥?b>3, respectively, indicating the dominant effect of the coordination geometry of the spin carrier, instead of the f鈥揻 interaction, on the magnetic properties. The present result will be helpful for the future design and synthesis of tetrapyrrole lanthanide SMMs with sandwich molecular structures.